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A fiber from the stems is a hemp substitute; it is used to make thread, cordage and coarse fabrics. It is also used for stuffing pillows and the smaller stems are used in basket making. It also has medicinal properties: the young herbaceous tips of flowering shoots, harvested in spring, are cardiotonic, emetic and purgative; the entire plant is an efficacious and potent diuretic. For the same purposes, the seeds can also be used (3). Spartium junceum is an unsafe herb, because of the cytisine content, causing serious intoxication. Recently, the production and distribution of alkaloids has been investigated in the different plant parts, at different stages of its life cycle (4,5). Yesilada et al. recorded the utilization of a flower infusion for the treatment of gastric ulcers in southern Anatolia (6); a recent study on S. junceum justified this traditional use, demonstrating the potent anti-ulcerogenic activity of the flowers, due to the presence of an oleanene-type saponin (7). Spartiumjunceum is also commonly called "fragrant broom" because its flowers are fairly fragrant (8); they contain an oil, even if in low quantity. oil from the flowers is used in perfumery in order to have a complex mixture together with other essential oils or isolated components (9). Until 1980, almost nothing was known about the chemical composition of genet. In that year, Shibainoto et al. (10) reported the chemical composition of the absolute. In the following years, Joulain (11) and Maupetit (12) described chemical constituents of genet by means of a static headspace analysis and by means of several fractionation techniques, combined with modern Chromatographie and spectroscopic techniques, respectively. In this paper we present the major constituents of flower oil obtained by hydrodistillation from Tuscan specimens of Spartiumjunceum. Materials and Methods The analyses were carried out on samples of S. junceum fresh flowers, collected in full blooming in south-central Tuscany from wild plants found in hill country. Vouchers, identified by E. Miraldi, were deposited in the Herbarium of Siena University, Italy (SIENA). Fresh flowers of S. junceum ( 100 g) were hydrodistilled for 4 h using a circulatory Clevenger-type apparatus; the oil yield was very low ( Analytical GC was carried out using a Varian CP-3800 GC equipped with an FID detector (T 230°C) or coupled with a Varian Saturn 2000 Ion Trap Mass Spectrometer (Varian, Walnut Creek, CA). A DB-5 column (30 m × mm, µm film thickness, Supelco Inc., Bellefonte, PA) was employed, with helium as carrier gas (flow rate mL/min). Samples were injected using the split sampling technique, ratio 1:50; sample amount injected was µL; injection port temperature 250°C. Oven temperature was held at 50°C for 2 min, then programmed at 5°C/min up to 250°C, held there for 10 min and then again programmed at 10°C/min to 300°C. The MS operating parameters were: electron ionization 70 eV; source temperature 150°C; scan range 40-650 amu. Identification of the constituents was carried out by comparing the retention times with those of reference compounds and peak-matching library search using the NBS/NIST and the LIBR(TP) libraries, and comparison of the MS data with those published in references works (13-15). Quantitative data were obtained from electronic integration of FID areas without the use of correction factors. Results and Discussion The volatile components identified in samples oil are listed in Table I, together with the relative percentages, in order of their elution from the column. The values are expressed as the mean of at least three determinations. Spartium junceum flowers are the source of an oil recommended for perfumery, though it is little used. The flowers have a fragrance that has been likened to oranges (16), so that it has been suggested to fit into the orange flower compound (17), The perfume industry prefers to use the absolute, because it has an intensely sweet, floral haylike fragrance (12), which blends well with vanilla, tobacco and violet fragrances. As can be seen in Table I, hydrocarbons were the main components of the oil; in fact tricosane (%), tetracosane (%) and pentacosane (%) constituted altogether almost 48% of total oil composition. These compounds are widely diffused in the vegetable kingdom (18). As is well known, volatiles constitute an important aspect governing the sensitivity of the insects in host selection. Kairomonal compounds, like tricosane, tetracosane and pentacosane, are host-seeking stimulants for the egg parasite (19), so that kairomones can be employed in manipulating entomophagous activity in biocontrol programs (20). Analyses of volatiles of cotton flowers revealed that in addition to their nutritional quality, kairomonal compounds act as attractant resources for many of the parasitoids (21). Octadecanyl acetate (stearyl acetate) was found in a remarkable amount (%); previously, it has been isolated from plants and insects and also from human sebaceous lipids, and it is reported as being used in many cosmetic formulations. For what concerns the other minor constituents of S. junceum oil, we found tetradecanol (myristic alcohol) and octanol only in traces, while the relative acids have been found in the absolute (10). The oil composition of S. junceum is of academic interest, with little commercial importance. However, further studies are requested on the quality evaluation of oil of this species in order to determine its commercial application in comparison with its absolute. Acknowledgements This work was supported in part by M. .. (Ministero dell'Unwersità e della Ricerca Scientifica e Tecnologica), Rome. References 1. . Heywood, Spartiumjunceum. In: Flora Europaea. Edits., . Tutin, . Heywood, . Burges, . Moore, . Valentine, . Walters and . Webb, vol. 2, p 101, Cambridge Press, Cambridge (1976). 2. A. Huxley, M. Griffiths and M. Levy, The New Royal Horticultural Society Dictionary of Gardening, vol. 4, p 345, The Macmillan Press, London (1992). 3. P. Gastaldo, Compendio della Flora Officinale ltaliana. p 160. Piccin, Padova (1987). 4. L. Barboni, A. Manzi, B. Bellomariaand . Quinto, Alkaloid content in four Spart/um junceum populations as a defensive strategy against predators. Phytochemistry, 37, 1197-1200 (1994). 5. G. Lurz, R. Greinwald, L. Witte and . Czygan, Quinolizidine alkaloids in Spartiumjunceum. Planta Med., 56, 522-525 (1990). 6. E. Yesilada, I. Gürbüz and H. Shibata, Screening of Turkish anti-ulcerogenic folk remedies for anti-Helicobacter pylori activity. J. Ethnopharmacol., 66, 289-293 (1999). 7. E. Yesilada and T. Yoshihisa, A saponin with anti-ulcerogenic effect from the flowers of Spartium junceum. Phytochemistry, 51, 903-908 (1999). 8. R. Longo, LeMonografie Tedesche, Schede Fitoterapiche del Ministero della Sanità di Germania, Versione ltaliana Tradotta e Commentata. Studio Edizioni, Milano (1994-1996). 9. J. Bruneton, Pharmacognosie, Phytochimie, Plantes Médicinales, p 689, Technique et Documentation-Lavoisier, Parigi (1993). 10. T. Shibamoto, K. Yamaguchi and K. Harada, Chemical constituents of genet. Paper 142, 8th international Essential oils Congress, Cannes (1980). 11. D. Joulain, Studyofthe fragrance given off by certain springtime flowers. In: Progress in Essential oil Research. Edit., EJ. Brunke, Walter de Gruyter, Berlin (1986). 12. P. Maupetit, Noveauxconstituents de l'absolue genet (Spartiumjunceum L). Rivista ltal. EPPOS (numero speciale), 325-343 (1992). 13. . Adams, Identification of Essential oils by Ion Trap Mass Spectroscopy. Academic Press, San Diego (1989). 14. W. Jennings and T Shibamoto, Qualitative Analysis of Flavor and Fragrance Volatiles by Glass Capillary Gas Chromatography. Academic Press, New York (1980). 15. . Adams, Identification of Essential oil Components by Gas Chromatography/Mass Spectroscopy. Allured Publishing Corporation, Carol Stream, IL (1995). 16. R. Genders, Scented Flora of the World. Robert Hale, London (1994). 17. .T. Uphof, Dictionary of Economic Plants. Verlag von J. Cramer, Lehre (1968). 18. G. Fenaroli, Le Sostanze Aromatiche, Sostanze Aromatiche Naturali. Ulrico Hoepli, Milano (1963). 19. . Jones, WJ. Lewis, M. Beroza, . Bierl and . Sparks, Host-seeking stimulants (kairomones) forthe egg parasite. Environ. Entomol., 2, 593-596 (1973). 20. WJ. Lewis, . Nordlund, . Gueldner, .A. Teal and . Tumlinson, Kairomones andtheiruse for management ofentomophagous insects. J. Chem. Ecol., 8, 1323-1331 (1982). 21. HJ. Williams, . Elzen and . Vinson, Novel Aspects of Insect-Plant Interaction. Edits., P. Barbosa and . Letourneu, pp 171-200, John Wiley, New York (1998). Elisabetta Miraldi* and Sara Ferri Dipartimento di Scienze Ambientali "G. Sarfatti," Sezione Eiologia Farmaceutica, Università degli Studi dl Siena, Via . Mattioli 4, 53100 Siena, Italy Gianluca Giorgi Centra Interdipartimentale di Analisi e Determinazione Strutturale (CIADS), Università degli Studi di Siena, Via A. Moro, 53100 Siena, Italy "Address for correspondence Received: July 2002 Revised: November 2002 Accepted: January 2003 1041-2905/04/0006-0568$/0-©2004 Allured Publishing Corp.
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